Oxidative carbonylation of methane to acetic acid on an Fe-modified ZSM-5 zeolite

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 329, P. 122549 - 122549

Published: March 1, 2023

Language: Английский

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Sustainable Energy Resources for Driving Methane Conversion

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(36)

Published: Aug. 13, 2023

Abstract The conversion of methane to value‐added chemicals by traditional reforming processes suffers from intensive energy consumption due its particularly strong C─H bonds. Thus, it is urgent optimize the driving force structure for accelerating integration sustainable energy. In this review, advances in energy‐driven are systematically summarized provide a scientific understanding operation/storage concepts, reactor design, technological maturity, system optimization, and remaining issues. Furthermore, essence, economic evaluations, balance, social impacts driven carefully discussed, paving path future course research development. Diversifying mix can play an important role industries, being used as crucial step transition energy, especially combination solar/nuclear with fossil fuels produce chemicals. Additionally, review intends bridge studies development, ultimate goal offering robust framework understand current status guidance design solutions greener future.

Language: Английский

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Oxidative-Atmosphere-Induced Strong Metal–Support Interaction and Its Catalytic Application

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(8), P. 911 - 923

Published: April 3, 2023

ConspectusIn 1978, the classical strong metal-support interaction (C-SMSI) was first explored by observing significantly suppressed H2 and CO adsorption on Group-VIII noble-metal-reducible oxide systems after high-temperature treatment. Subsequent studies showed that local electron redistribution encapsulation overlayers metal nanoparticles (NPs) are typical features of SMSI, which endows supported heterogeneous catalysts with various advantageous properties for catalytic applications. In recent decades, significant advancements have been made in utilization SMSI effects via oxidation, adsorbate mediation, wet-chemistry processes, so on. Oxidative (O-SMSI) observed Mou et al. Au/ZnO, wherein were formed Au NPs being treated under oxidative conditions. this system, positively charged through transfer from to support, Au-O-Zn linkages drive formation overlayer. O-SMSI behavior it imparts catalyst contradict our previous understanding C-SMSI respect need a reducing atmosphere known driving force. Moreover, show considerable stability oxidizing atmospheres provide potential solution problem sintering catalysts. To date, has supports, including oxides, phosphides, nitrides, provides application opportunities process.In Account, we briefly introduce research background motivation developing new exhibiting effect. particular, Au/hydroxyapatite (HAP, nonoxide) system induced applying oxidation prevents NPs. Furthermore, Pt Pd exhibit HAP ZnO supports heat Based composition structure HAP, tetrahedral units ((PO4)3-) OH- shown be responsible O-SMSI. Importantly, electronic (i.e., support), is characteristic feature O-SMSI, can controlled tailor strength interaction. We used exogenous adsorbents tune state (Fermi level) artificially Au, Pd, Pt, Rh TiO2. findings study indicate broadly applied development Finally, summarize some common different proposed mechanisms insights into existing challenges possible directions field.

Language: Английский

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Selective Formation of Acetic Acid and Methanol by Direct Methane Oxidation Using Rhodium Single-Atom Catalysts

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11415 - 11419

Published: May 12, 2023

Atomically dispersed catalysts such as single-atom have been shown to be effective in selectively oxidizing methane, promising a direct synthetic route value-added oxygenates acetic acid or methanol. However, an important challenge of this approach has that the loading active sites by is low, leading low overall yield products. Here, we report can address issue. It utilizes metal-organic framework built with porphyrin linker, which provides high concentrations binding support atomically rhodium. up 5 wt% rhodium achieved excellent dispersity. When used for synthesis methane oxidation, new benchmark performance 23.62 mmol·gcat-1·h-1 was measured. Furthermore, catalyst exhibits unique sensitivity light, producing (under illumination, 66.4% selectivity) methanol (in dark, 65.0% under otherwise identical reaction conditions.

Language: Английский

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Efficient catalysts of surface hydrophobic Cu-BTC with coordinatively unsaturated Cu(I) sites for the direct oxidation of methane

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(10)

Published: Feb. 27, 2023

Selective oxidation of methane to organic oxygenates over metal–organic frameworks (MOFs) catalysts at low temperature is a challenging topic in the field C1 chemistry because inferior stability MOFs. Modifying surface Cu-BTC via hydrophobic polydimethylsiloxane (PDMS) 235 °C under vacuum not only can dramatically improve its catalytic cycle liquid phase but also generate coordinatively unsaturated Cu(I) sites, which significantly enhances activity catalyst. The results spectroscopy characterizations and theoretical calculation proved that sites made H 2 O dissociative into •OH, formed Cu(II)-O active species by combining with for activating C−H bond methane. high productivity (CH 3 OH CH OOH) 10.67 mmol g cat. −1 h super selectivity 99.6% was achieved Cu-BTC-P-235 catalyst, catalyst possessed excellent reusability.

Language: Английский

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Contact‐Electro‐Catalysis for Direct Oxidation of Methane under Ambient Conditions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 16, 2024

Abstract The conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo‐ and electro‐ chemical processes, challenges such as complex catalyst design, costly oxidants, unwanted byproducts remain. This study exploits the concept contact‐electro‐catalysis, initiating reactions through charge exchange at a solid–liquid interface, to report novel process for directly converting conditions. Utilizing electrification commercially available Fluorinated Ethylene Propylene (FEP) with water ultrasound, we demonstrate how this interaction promote activation molecules. Our results show that yield HCHO CH 3 OH can reach 467.5 151.2 μmol ⋅ g cat −1 , respectively. We utilized electron paramagnetic resonance (EPR) confirm evolution hydroxyl radicals (⋅OH) superoxide (⋅OOH). Isotope mass spectrometry (MS) was employed analyze elemental origin OH, which be further oxidized HCHO. Additionally, conducted density functional theory (DFT) simulations assess reaction energies FEP H 2 O, O 4 these implications methodology, its potential applicability wider array gas‐phase catalytic reactions, underscore advance in catalysis.

Language: Английский

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Methane Bubbled Through Seawater Can be Converted to Methanol With High Efficiency

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 21, 2025

Partial oxidation of methane (POM) is achieved by forming air-methane microbubbles in saltwater to which an alternating electric field applied using a copper oxide foam electrode. The solubility increased putting it contact with water containing dissolved KCl or NaCl (3%). Being fully dispersed as (20-40 µm diameter), reacts more hydroxyl radicals (OH·) at the gas-water interface. voltage (100 mV) generates two synergistic POM processes dominated Cl- → Cl· + e- and O2 -• under positive negative potentials, respectively. By tuning frequency amplitude, extent path process can be precisely controlled so that than 90% methanol selectively formed compared byproducts, dichloromethane, acetic acid. conversion yield estimated 57% rate approximately 887 µM h-1. This method appears have potential for removing from air seawater converting higher-concentration sources into value-added methanol.

Language: Английский

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NiO/ZnO heterojunction nanorod catalyst for high-efficiency electrochemical conversion of methane

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 323, P. 122129 - 122129

Published: Nov. 9, 2022

Language: Английский

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Clever Nanomaterials Fabrication Techniques Encounter Sustainable C1 Catalysis

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(17), P. 2341 - 2353

Published: Aug. 14, 2023

ConspectusC1 catalysis, which refers to the conversion of molecules with a single carbon atom, such as CO, CO2, and CH4, into clean fuels basic building blocks for chemical industries, has built bridge between resource utilization valuable supply. With respect goal neutrality, C1 catalysis also plays an essential role owing its integrated functions in green catalytic process fewer CO2 emissions even direct high-value-added greenhouse gases (CO2 CH4). However, inert nature C–O or C–H bond well uncontrollable C–C coupling render challenging. The rational design highly active materials (denoted catalysts) strong capacities activation by convenient nanomaterials fabrication methods boost performance molecule conversion, including targeted product selectivity long-term stability, is cornerstone catalysis.Notably, familiar concepts heterogeneous tandem confinement are applicable have been successfully used catalyst. Regarding concept that integrates multiple reactions single-pass via bi- multifunctional catalyst, it promising shed new light on oriented molecules, especially C2+ hydrocarbon oxygenate synthesis. effect powerful controlling distribution enhancing efficiency bonds due unique reactants/intermediate adsorption evolution behaviors confined interface special electronic environment. Moreover, metal–support interactions (MSIs), properties site, engineering issues susceptible performance. Therefore, under guidance novel rules innovation aid advanced techniques always hot research topic catalysis.In this Account, we briefly describe challenges thermal–catalytic (mainly CH4) conversion. At same time, synergistic functioning physicochemical highlighted. More importantly, summarize our progress rationally designing tailor-made catalysts enhance techniques, traditional wet-chemistry strategies, magnetron sputtering method, 3D printing technology. Specifically, ingenious capsule catalyst ammonia pools zeolites fabricated wet chemistry possess extraordinary transformation CH4 molecules. Also, method reliable modulating metallic sites thereby tailoring final selectivity. Furthermore, showcase capability metal technology fabricating self-catalytic reactor, reaction field nanoscale integrated. Finally, predict future opportunities efficient assistance clever techniques.

Language: Английский

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Selective Oxidation Using In Situ-Generated Hydrogen Peroxide

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 57(1), P. 106 - 119

Published: Dec. 20, 2023

ConspectusHydrogen peroxide (H2O2) for industrial applications is manufactured through an indirect process that relies on the sequential reduction and reoxidation of quinone carriers. While highly effective, production typically centralized entails numerous energy-intensive concentration steps. Furthermore, overhydrogenation necessitates periodic replacement, leading to incomplete atom efficiency. These factors, in addition presence propriety stabilizing agents concerns associated with their separation from product streams, have driven interest alternative technologies chemical upgrading. The decoupling oxidative transformations commercially synthesized H2O2 may offer significant economic savings a greenhouse gas emissions several industrially relevant processes. Indeed, utilization oxidant situ, elements, would represent positive step toward more sustainable synthesis sector, offering potential total efficiency, while avoiding drawbacks current routes, which are inherently linked commercial production. Such perhaps now pertinent than ever given rapidly improving viability green hydrogen production.The application situ-generated has been long-standing goal feedstock valorization, most placed propylene epoxidation. Until very recently viable situ processes lacking, prior approaches hindered by low rates conversion or poor selectivity desired products, often resulting competitive hydrogenation reactions. Based over 20 years research, led development catalysts direct high >99% H2 utilization, we turned our attention range where generated utilized situ. demonstrated it possible rival state-of-the-art synthesis, establishing intensification considerable decarbonization sector.We further established route both bulk fine chemo-catalytic/enzymatic one-pot approach, heterogeneous surfaces subsequently class unspecific peroxygenase enzymes C–H bond functionalization. Strikingly, careful control chemo-catalyst, ensure competitive, nonenzymatic pathways inhibited also regiospecific processes, cost operation chemo-enzymatic approach at near-ambient temperatures pressures. Beyond traditional chemo-catalysis, efficacy (and oxygen-based radical species) remediation environmental pollutants major laboratory, such technology improvements conventional disinfection processes.We hope this Account, highlights key contributions laboratory field recent years, demonstrates chemistries be unlocked improved upon via inspires broader scientific community.

Language: Английский

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